Atomically dispersed Mn–N_x catalysts derived from Mn-hexamine coordination frameworks for oxygen reduction reaction

Abstract

Metal-organic frameworks recently have been burgeoning and used as precursors to obtain various metal–nitrogen–carbon catalysts for oxygen reduction reaction (ORR). Although rarely studied, Mn–N–C is a promising catalyst for ORR due to its weak Fenton reaction activity and strong graphitization catalysis. Here, we developed a facile strategy for anchoring the atomically dispersed nitrogen-coordinated single Mn sites on carbon nanosheets (MnNCS) from an Mn-hexamine coordination framework. The atomically dispersed Mn–N₄ sites were dispersed on ultrathin carbon nanosheets with a hierarchically porous structure. The optimized MnNCS displayed an excellent ORR performance in half-cells (0.89 V vs. reversible hydrogen electrode (RHE) in base and 0.76 V vs. RHE in acid in half-wave potential) and Zn–air batteries (233 mW cm⁻² in peak power density), along with significantly enhanced stability. Density functional theory calculations further corroborated that the Mn–N₄–C₁₂ site has favorable adsorption of *OH as the rate-determining step. These findings demonstrate that the metal-hexamine coordination framework can be used as a model system for the rational design of highly active atomic metal catalysts for energy applications.

Keywords

carbon nanosheets / electrocatalyst / metal-organic frameworks / Mn–N₄ / oxygen reduction reaction / Zn–air batteries

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